CN109181654B - Graphene-based composite heat-conducting film and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a preparation method of a graphene-based composite heat-conducting film, which comprises the following steps: (1) adding flake graphite into an oxidant solvent, carrying out ultrasonic stirring stripping, adding sodium lauryl sulfate and lauryl sulfuric acid monoethanolamine, stirring, and carrying out microwave irradiation treatment to obtain a graphene oxide solution; (2) taking hollow carbon nanospheres, dispersing the hollow carbon nanospheres in a mixed solvent, and then heating and refluxing to obtain surface-modified hollow carbon nanospheres; (3) adding the modified carbon nanospheres into the graphene oxide solution, and uniformly stirring; spraying the obtained mixed solution onto a flexible substrate by adopting a thermal spraying method, and depositing to obtain a graphene oxide composite film; (4) reducing the graphene oxide composite film; (5) and calcining the reduced graphene-based composite film to obtain the graphene composite heat-conducting film. The graphene-based composite heat-conducting film prepared by the invention has excellent heat-conducting property, good stability and wide application prospect.
Description
Technical Field
The invention belongs to the technical field of graphene materials and application thereof, and particularly relates to a graphene-based composite heat-conducting film and a preparation method and application thereof.
Background
Along with the progress of science and technology, electronic equipment gradually to little miniaturization, component integration, frivolousization, performance high efficiency development, however electronic equipment can produce a large amount of heats at the operation in-process, if can not in time effectively derive the heat, not only can influence its stability, can shorten its life greatly moreover, therefore must use the heat sink material to improve heat transfer efficiency, eliminate the focus and gather, give off the heat fast, reduce the equipment temperature, make its lasting high-efficient operation. The traditional heat dissipation material has high density, low heat conductivity and complex processing, and is difficult to meet the modern heat dissipation requirement, so that the requirement on heat dissipation is met by a low-density high-heat-conductivity material.
Graphene (Graphene) is a polymer made of carbon atoms in sp2Hexagonal honeycomb crystal formed by hybrid tracksA single layer planar film of an array of cells (honeycomb crystals) having only one carbon atom thick of two-dimensional material. Graphene is currently the thinnest and hardest nanomaterial in the world, and is almost completely transparent, absorbing only 2.3% of light; the heat conductivity coefficient is as high as 5300W/m.K, higher than that of carbon nano tube and diamond, and its electron mobility is over 15000cm at normal temp2V.s, and is higher than carbon nanotubes or silicon crystals and has a resistivity of about 10-6Omega cm, lower than copper or silver, is the material with the smallest resistivity in the world. Graphene has such excellent physicochemical properties and has been gradually used in the fields of transparent conductive films, nano electronic devices (transistors, transistor circuit interconnection memory semiconductors), conductive inks, solar cells, batteries, supercapacitors, sensors, biomedicines, and the like.
In chinese patent CN104592950A, graphene nanoplatelets and high molecular polymer are mixed into a film, and the film is carbonized and then graphitized to obtain a high thermal conductivity graphene-based polymer thermal conductive film. The Chinese patent CN104264146A uses a functionalized graphene solution to coat a film on a substrate, and the film is dried and then treated at a high temperature of 2800 ℃ under 1000 ℃ to obtain the functionalized graphene-based transparent conductive and heat-conducting film. The Chinese patent CN105523547A obtains the ultra-flexible high-thermal-conductivity graphene film through the steps of graphene oxide solution film forming, chemical reduction, high-temperature reduction, high-pressure pressing and the like. In chinese patent CN105110794A, the pretreated graphene oxide is coated on a PET film to be carbonized and graphitized to obtain a graphene film. In the chinese patent CN105502368A, graphene oxide is scraped on a substrate, and then graphitized, rolled, and the substrate is peeled to obtain a graphene thin film. Chinese patent CN104085143A is to spray a graphene oxide solution on a flexible substrate, and then prepare a graphene heat-conducting film by a reduction method.
However, the graphene thermal conductive film has some defects and shortcomings, such as insufficient thermal conductivity, and the spraying method needs to use an adhesive to enhance the bonding strength with the substrate, so that it is of great importance to develop a graphene film with high thermal conductivity and stable performance.
Disclosure of Invention
The invention aims to provide a graphene-based composite heat-conducting film and a preparation method thereof, the preparation method is simple in process and controllable in conditions, the condensation among graphene can be effectively reduced, the internal defects of the graphene are reduced, and the obtained product is stable in performance and excellent in heat dissipation performance.
In order to realize the purpose, the preparation process adopted by the invention comprises the following steps:
a preparation method of a graphene-based composite heat conduction film comprises the following steps:
(1) preparing a graphene oxide solution: adding crystalline flake graphite into a mixed solvent of concentrated sulfuric acid and potassium permanganate for ultrasonic stirring stripping, then adding sodium lauryl sulfate and monoethanolamine dodecyl sulfate, stirring for a period of time, then performing microwave irradiation treatment for a period of time, and finally adding deionized water, washing and performing suction filtration to obtain a graphene oxide solution;
(2) preparing modified carbon nanospheres: dispersing hollow carbon nanospheres in a mixed solvent of ethylene glycol monoethyl ether and ethyl acetate, heating and refluxing for 3-5h, centrifuging, washing and filtering after the reaction is finished to obtain surface-modified hollow carbon nanospheres;
(3) adding the modified carbon nanospheres prepared in the step (2) into the graphene oxide solution in the step (1), and uniformly stirring; then spraying the obtained mixed solution onto a flexible substrate by adopting a thermal spraying method, and depositing to obtain a graphene oxide composite film;
(4) reducing the graphene oxide composite film obtained in the step (3) to obtain a graphene-based composite film;
(5) and (4) heating the graphene-based composite film obtained by reduction in the step (4) to 600-1000 ℃ at the speed of 1-3 ℃/min, and preserving heat for 2-4h, and then cooling to room temperature to obtain the graphene composite heat-conducting film.
Preferably, the mass ratio of the concentrated sulfuric acid to the potassium permanganate to the crystalline flake graphite in the step (1) is 3-6: 150-250: 10-40 parts of; the addition amount of the sodium lauryl sulfate and the monoethanolamine dodecyl sulfate is 0.5 to 3 percent of the mass of the flake graphite.
Preferably, the ultrasonic stirring stripping time in the step (1) is 0.5-3h, the power of microwave irradiation is 700-900W, and the time is 5-15 min.
Preferably, the diameter of the carbon nanospheres in the step (2) is 10-40nm, and the mass-to-volume ratio g/mL of the carbon nanospheres to the mixed solvent is 1: 40-80; the volume ratio of the ethylene glycol monoethyl ether to the ethyl acetate in the mixed solvent is 1: 1.
Preferably, the addition amount of the modified carbon nanospheres in the step (3) is 5-10% of the graphene oxide solution.
Preferably, the height of the thermal spraying in the step (3) is 50-70cm from the substrate, and the temperature of the spraying is 80-160 ℃.
Preferably, the method for reducing the graphene oxide composite film in the step (4) comprises the following steps: introducing H at 1000 deg.C in a vacuum tube furnace2And reducing to obtain the graphene-based composite film.
Preferably, the flexible substrate is a copper foil or an aluminum foil.
In addition, the invention also claims the graphene-based composite heat-conducting film prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the method, firstly, the crystalline flake graphite is subjected to ultrasonic stripping through strong oxidation to obtain graphene oxide, then the graphene oxide is subjected to functional group modification and then subjected to microwave radiation secondary stripping, thinner graphene can be obtained through 2 times of stripping, and the dispersibility of the graphene oxide in a solvent and the uniformity of a spraying liquid on a substrate can be effectively improved due to the introduction of functional groups such as hydroxyl, carboxyl and the like;
(2) according to the invention, the nano carbon spheres are added into the graphene oxide solution to form the composite spraying liquid, so that on one hand, the heat dissipation capability of the graphene is enhanced by utilizing the high heat conductivity of the carbon spheres, and on the other hand, the carbon spheres can be distributed among the lamellar layers of the graphene due to the small size effect of the carbon spheres, so that the heat conduction path of the graphene is smooth, a stable and uniform heat conduction network is formed, and the heat transfer efficiency is improved;
(3) according to the invention, the graphene-based composite film is subjected to high-temperature treatment, so that the defects of graphene can be effectively repaired, the heat conduction path of the graphene-based composite material is further improved, and the stability of the graphene-based composite material is improved.
Drawings
Fig. 1 is an SEM image of the graphene-based composite heat conductive film prepared in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a graphene-based composite heat conduction film comprises the following steps:
(1) preparing a graphene oxide solution: adding 2g of flake graphite into a mixed solvent of 1g of concentrated sulfuric acid and 40g of potassium permanganate, ultrasonically stirring and stripping for 1h, then adding 0.01g of sodium lauryl sulfate 0.01g of monoethanolamine dodecyl sulfate, stirring for 0.5h, then carrying out microwave irradiation treatment for 10min, and finally adding deionized water, washing and carrying out suction filtration to obtain a graphene oxide solution;
(2) preparing modified carbon nanospheres: taking 0.2g of hollow carbon nanospheres, dispersing in a mixed solvent of 5mL of ethylene glycol monoethyl ether and 5mL of ethyl acetate, heating and refluxing for 4h, centrifuging, washing and filtering after the reaction is finished to obtain surface-modified hollow carbon nanospheres;
(3) adding the modified carbon nanospheres prepared in the step (2) into the graphene oxide solution in the step (1), and uniformly stirring; then spraying the obtained mixed solution on a copper foil substrate by adopting a thermal spraying method, and depositing to obtain a graphene oxide composite film; the spraying height is 60cm away from the substrate during thermal spraying, and the spraying temperature is 120 ℃;
(4) introducing H at 1000 deg.C in a vacuum tube furnace2Reducing to obtain a graphene-based composite film;
(5) and (4) heating the graphene-based composite film obtained by reduction in the step (4) to 800 ℃ at the speed of 2 ℃/min, preserving heat for 3 hours, and then cooling to room temperature to obtain the graphene composite heat-conducting film.
Example 2
A preparation method of a graphene-based composite heat conduction film comprises the following steps:
(1) preparing a graphene oxide solution: adding 2g of flake graphite into a mixed solvent of 1g of concentrated sulfuric acid and 40g of potassium permanganate, ultrasonically stirring and stripping for 1h, then adding 0.01g of sodium lauryl sulfate 0.01g of monoethanolamine dodecyl sulfate, stirring for 0.5h, then carrying out microwave irradiation treatment for 10min, and finally adding deionized water, washing and carrying out suction filtration to obtain a graphene oxide solution;
(2) preparing modified carbon nanospheres: taking 0.15g of hollow carbon nanospheres, dispersing in a mixed solvent of 4.5mL of ethylene glycol monoethyl ether and 4.5mL of ethyl acetate, heating and refluxing for 4h, and after the reaction is finished, centrifuging, washing and filtering to obtain surface-modified hollow carbon nanospheres;
(3) adding the modified carbon nanospheres prepared in the step (2) into the graphene oxide solution in the step (1), and uniformly stirring; then spraying the obtained mixed solution on a copper foil substrate by adopting a thermal spraying method, and depositing to obtain a graphene oxide composite film; the spraying height is 60cm away from the substrate during thermal spraying, and the spraying temperature is 100 ℃;
(4) introducing H at 1000 deg.C in a vacuum tube furnace2Reducing to obtain a graphene-based composite film;
(5) and (4) heating the graphene-based composite film obtained by reduction in the step (4) to 1000 ℃ at the speed of 2 ℃/min, preserving heat for 3 hours, and then cooling to room temperature to obtain the graphene composite heat-conducting film.
Example 3
A preparation method of a graphene-based composite heat conduction film comprises the following steps:
(1) preparing a graphene oxide solution: adding 2g of flake graphite into a mixed solvent of 0.6g of concentrated sulfuric acid and 20g of potassium permanganate, ultrasonically stirring and stripping for 1h, then adding 0.02g of sodium lauryl sulfate 0.02g of monoethanolamine dodecyl sulfate, stirring for 0.5h, then carrying out microwave irradiation treatment for 10min, and finally adding deionized water, washing and carrying out suction filtration to obtain a graphene oxide solution;
(2) preparing modified carbon nanospheres: taking 0.2g of hollow carbon nanospheres, dispersing in a mixed solvent of 5mL of ethylene glycol monoethyl ether and 5mL of ethyl acetate, heating and refluxing for 4h, centrifuging, washing and filtering after the reaction is finished to obtain surface-modified hollow carbon nanospheres;
(3) adding the modified carbon nanospheres prepared in the step (2) into the graphene oxide solution in the step (1), and uniformly stirring; then spraying the obtained mixed solution on a copper foil substrate by adopting a thermal spraying method, and depositing to obtain a graphene oxide composite film; the spraying height is 70cm away from the substrate during thermal spraying, and the spraying temperature is 160 ℃;
(4) introducing H at 1000 deg.C in a vacuum tube furnace2Reducing to obtain a graphene-based composite film;
(5) and (4) heating the graphene-based composite film obtained by reduction in the step (4) to 800 ℃ at the speed of 2 ℃/min, preserving heat for 4h, and then cooling to room temperature to obtain the graphene composite heat-conducting film.
Example 4
A preparation method of a graphene-based composite heat conduction film comprises the following steps:
(1) preparing a graphene oxide solution: adding 2g of flake graphite into a mixed solvent of 0.6g of concentrated sulfuric acid and 24g of potassium permanganate, ultrasonically stirring and stripping for 1h, then adding 0.02g of sodium lauryl sulfate 0.02g of monoethanolamine dodecyl sulfate, stirring for 0.5h, then carrying out microwave irradiation treatment for 10min, and finally adding deionized water, washing and carrying out suction filtration to obtain a graphene oxide solution;
(2) preparing modified carbon nanospheres: taking 0.2g of hollow carbon nanospheres, dispersing in a mixed solvent of 5mL of ethylene glycol monoethyl ether and 5mL of ethyl acetate, heating and refluxing for 4h, centrifuging, washing and filtering after the reaction is finished to obtain surface-modified hollow carbon nanospheres;
(3) adding the modified carbon nanospheres prepared in the step (2) into the graphene oxide solution in the step (1), and uniformly stirring; then, spraying the obtained mixed solution on an aluminum foil substrate by adopting a thermal spraying method, and depositing to obtain a graphene oxide composite film; the spraying height is 60cm away from the substrate during thermal spraying, and the spraying temperature is 120 ℃;
(4) introducing H at 1000 deg.C in a vacuum tube furnace2Reducing to obtain a graphene-based composite film;
(5) and (4) heating the graphene-based composite film obtained by reduction in the step (4) to 800 ℃ at the speed of 2 ℃/min, preserving heat for 3 hours, and then cooling to room temperature to obtain the graphene composite heat-conducting film.
Example 5
A preparation method of a graphene-based composite heat conduction film comprises the following steps:
(1) preparing a graphene oxide solution: adding 2g of flake graphite into a mixed solvent of 1g of concentrated sulfuric acid and 40g of potassium permanganate, ultrasonically stirring and stripping for 1h, then adding 0.01g of sodium lauryl sulfate 0.01g of monoethanolamine dodecyl sulfate, stirring for 0.5h, then carrying out microwave irradiation treatment for 10min, and finally adding deionized water, washing and carrying out suction filtration to obtain a graphene oxide solution;
(2) preparing modified carbon nanospheres: taking 0.1g of hollow carbon nanospheres, dispersing in a mixed solvent of 3mL of ethylene glycol monoethyl ether and 3mL of ethyl acetate, heating and refluxing for 4h, and after the reaction is finished, centrifuging, washing and filtering to obtain surface-modified hollow carbon nanospheres;
(3) adding the modified carbon nanospheres prepared in the step (2) into the graphene oxide solution in the step (1), and uniformly stirring; then, spraying the obtained mixed solution on an aluminum foil substrate by adopting a thermal spraying method, and depositing to obtain a graphene oxide composite film; the spraying height is 50cm away from the substrate during thermal spraying, and the spraying temperature is 100 ℃;
(4) introducing H at 1000 deg.C in a vacuum tube furnace2Reducing to obtain a graphene-based composite film;
(5) and (4) heating the graphene-based composite film obtained by reduction in the step (4) to 900 ℃ at the speed of 2 ℃/min, preserving heat for 3h, and then cooling to room temperature to obtain the graphene composite heat-conducting film.
Comparative example 1
A preparation method of a graphene-based composite heat conduction film comprises the following steps:
(1) preparing a graphene oxide solution: adding 2g of flake graphite into a mixed solvent of 1g of concentrated sulfuric acid and 40g of potassium permanganate, ultrasonically stirring and stripping for 1h, then adding 0.01g of sodium lauryl sulfate 0.01g of monoethanolamine dodecyl sulfate, stirring for 0.5h, then carrying out microwave irradiation treatment for 10min, and finally adding deionized water, washing and carrying out suction filtration to obtain a graphene oxide solution;
(2) spraying the graphene oxide solution prepared in the step (1) onto a copper foil substrate by adopting a thermal spraying method, and depositing to obtain a graphene oxide composite film; the spraying height is 60cm away from the substrate during thermal spraying, and the spraying temperature is 120 ℃;
(3) introducing H at 1000 deg.C in a vacuum tube furnace2Reducing to obtain a graphene film;
(4) and (4) heating the graphene film obtained by reduction in the step (3) to 800 ℃ at the speed of 2 ℃/min, preserving heat for 3h, and then cooling to room temperature to obtain the graphene composite heat-conducting film.
Comparative example 2
A preparation method of a graphene-based composite heat conduction film comprises the following steps:
(1) preparing a graphene oxide solution: adding 2g of flake graphite into a mixed solvent of 1g of concentrated sulfuric acid and 40g of potassium permanganate, ultrasonically stirring and stripping for 1h, then adding 0.01g of sodium lauryl sulfate 0.01g of lauryl monoethanolamine sulfate, stirring for 0.5h, and finally adding deionized water, washing and suction-filtering to obtain a graphene oxide solution;
(2) preparing modified carbon nanospheres: taking 0.2g of hollow carbon nanospheres, dispersing in a mixed solvent of 5mL of ethylene glycol monoethyl ether and 5mL of ethyl acetate, heating and refluxing for 4h, centrifuging, washing and filtering after the reaction is finished to obtain surface-modified hollow carbon nanospheres;
(3) adding the modified carbon nanospheres prepared in the step (2) into the graphene oxide solution in the step (1), and uniformly stirring; then spraying the obtained mixed solution on a copper foil substrate by adopting a thermal spraying method, and depositing to obtain a graphene oxide composite film; the spraying height is 60cm away from the substrate during thermal spraying, and the spraying temperature is 120 ℃;
(4) introducing H at 1000 deg.C in a vacuum tube furnace2Reducing to obtain a graphene-based composite film;
(5) and (4) heating the graphene-based composite film obtained by reduction in the step (4) to 800 ℃ at the speed of 2 ℃/min, preserving heat for 3 hours, and then cooling to room temperature to obtain the graphene composite heat-conducting film.
Performance testing
The performance of the graphene thermal conductive films of examples 1 to 5 and comparative examples 1 to 2 was measured, and the results are shown in table 1 below:
| thermal conductivity (W/m. K) | Tensile Strength (MPa) | Film thickness (μm) | |
| Example 1 | 1930 | 84 | 15-22 |
| Example 2 | 1895 | 86 | 16-24 |
| Example 3 | 1916 | 92 | 18-22 |
| Example 4 | 1925 | 90 | 16-25 |
| Example 5 | 1933 | 87 | 15-24 |
| Comparative example 1 | 1219 | 70 | 20-28 |
| Comparative example 2 | 1458 | 80 | 38-56 |
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (7)
1. A preparation method of a graphene-based composite heat conduction film is characterized by comprising the following steps:
(1) preparing a graphene oxide solution: adding crystalline flake graphite into a mixed solvent of concentrated sulfuric acid and potassium permanganate for ultrasonic stirring stripping, then adding sodium lauryl sulfate and monoethanolamine dodecyl sulfate, stirring for a period of time, then performing microwave irradiation treatment for a period of time, and finally adding deionized water, washing and performing suction filtration to obtain a graphene oxide solution;
the ultrasonic stirring stripping time is 0.5-3h, the power of the microwave irradiation is 700-900W, and the time is 5-15 min;
(2) preparing modified carbon nanospheres: dispersing hollow carbon nanospheres in a mixed solvent of ethylene glycol monoethyl ether and ethyl acetate, heating and refluxing for 3-5h, and after the reaction is finished, centrifuging, washing and filtering to obtain surface-modified hollow carbon nanospheres;
the diameter of the carbon nanospheres is 10-40nm, and the mass volume ratio g/mL of the carbon nanospheres to the mixed solvent is 1: 40-80; the volume ratio of the ethylene glycol monoethyl ether to the ethyl acetate in the mixed solvent is 1: 1;
(3) adding the modified carbon nanospheres prepared in the step (2) into the graphene oxide solution in the step (1), and uniformly stirring; then spraying the obtained mixed solution onto a flexible substrate by adopting a thermal spraying method, and depositing to obtain a graphene oxide composite film;
(4) reducing the graphene oxide composite film obtained in the step (3) to obtain a graphene-based composite film;
(5) and (4) heating the graphene-based composite film obtained by reduction in the step (4) to 600-1000 ℃ at the speed of 1-3 ℃/min, and preserving heat for 2-4h, and then cooling to room temperature to obtain the graphene composite heat-conducting film.
2. The preparation method of the graphene-based composite heat-conducting film according to claim 1, wherein the mass ratio of the concentrated sulfuric acid, the potassium permanganate and the crystalline flake graphite in the step (1) is 3-6: 150-250: 10-40 parts of; the addition amount of the sodium lauryl sulfate and the monoethanolamine dodecyl sulfate is 0.5 to 3 percent of the mass of the flake graphite.
3. The preparation method of the graphene-based composite heat conduction membrane according to claim 1, wherein the modified carbon nanospheres in the step (3) are added in an amount of 5-10% of the graphene oxide solution.
4. The method for preparing the graphene-based composite heat-conducting film according to claim 1, wherein the spraying height in the thermal spraying in the step (3) is 50-70cm from the substrate, and the spraying temperature is 80-160 ℃.
5. The preparation method of the graphene-based composite heat conduction film according to claim 1, wherein the method for reducing the graphene oxide composite film in the step (4) comprises the following steps: introducing H at 1000 deg.C in a vacuum tube furnace2And reducing to obtain the graphene-based composite film.
6. The method for preparing the graphene-based composite heat-conducting film according to claim 1, wherein the flexible substrate is a copper foil or an aluminum foil.
7. The graphene-based composite heat conduction film prepared by the preparation method of any one of claims 1 to 6.
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| CN111944497B (en) * | 2019-05-16 | 2022-02-22 | 常州第六元素材料科技股份有限公司 | Graphene oxide composite carbon source mixture and preparation method thereof, graphene heat-conducting film and preparation method thereof |
| CN111908460A (en) * | 2020-07-06 | 2020-11-10 | 深圳市展旺新材料科技有限公司 | Preparation method of highly ordered and compact graphene heat-conducting film |
| CN115182022A (en) * | 2021-04-01 | 2022-10-14 | 浙江正泰电器股份有限公司 | Compound dispersant and preparation method thereof, and mixed electroplating solution and preparation method thereof |
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